Neutral and anionic transition metal complexes supported by decafluorodiphenylamido ligands: X-ray crystal structures of {Na(THF)2}{Ti[N(C6F5)2]4}, {K(η6-C6H5Me)2}{ZrCl2[N(C6F5)2]3}, K{VCl[N(C6F5)2]3}, Fe[N(C6F5)2]2(THF)2 and Co[N(C6F5)2]2(py)2
Reaction of MN(C6F5)2 (M=Na, K) with transition metal halides results in the formation of transition metal complexes incorporating decafluorodiphenylamido ligands. TiCl3(THF)3 reacts with 3 equiv. NaN(C6F5)2 to yield the ‘metallate’ complex {Na(THF)2}{Ti[N(C6F5)2]4} (1). Single crystal X-ray diffraction studies reveal a tetrahedral titanium center complexed by four decafluorodiphenylamido ligands; while two THF ligands and four fluorine atoms coordinate the sodium cation. ZrCl4 reacts with 3 equiv. KN(C6F5)2 to give {K(η6-C7H8)2}{ZrCl2[N(C6F5)2]3} (2). The 19F NMR spectrum of 2 reveals phenyl resonances in a 2:1 ratio, consistent with a trigonal bipyramidal structure being maintained in solution. The crystal structure of 2 reveals a pseudo-octahedral structure, with the sixth-coordination site being completed by a weak Zr–F interaction with a pentafluorophenyl group of an amido ligand. The potassium counterion interacts in an η6 fashion with two toluene rings in addition to a fluorine atom arising from one of the pentafluorophenyl groups. The reaction of VCl3 with 3 equiv. KN(C6F5)2 generates the ‘metallate’ complex K{VCl[N(C6F5)2]3} (3); the solid state structure of 3 reveals a distorted trigonal bipyramid with the coordination sphere being completed by a weak V–F interaction with the ortho-fluorine of one of the fluorophenyl amido ligands. Exposure of FeCl3 to 3 equiv. KN(C6F5)2 results in reduction of the metal center and the formation of the Fe(II) species Fe[N(C6F5)2]2(THF)2 (4). Compound 4 is tetrahedral in the solid state with none of the weak M–F contacts observed for 1, 2, 3 and 5. CoI2 reacts with 2 equiv. NaN(C6F5)2 in the presence of pyridine to produce the expected product Co[N(C6F5)2]2(py)2 (5); X-ray crystallography reveals a five-coordinate species in the solid state which is additionally stabilized by a weak Co–F interaction.
- Research Organization:
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- W-7405-ENG-36
- OSTI ID:
- 808293
- Report Number(s):
- LA-UR-02-4579
- Journal Information:
- Polyhedron, Vol. 22, Issue 1; ISSN 0277-5387
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
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